Nanoparticle-Containing Thermoplastic Composites and Methods of Preparing Same

ABSTRACT

High quality thermoplastic composites and composite laminates containing nanoparticles and/or nanofibers, and methods of producing such composites and laminates are disclosed. The composites comprise a thermoplastic polymer and a plurality of nanoparticles, and may include a fibrous structural reinforcement. The composite laminates are formed from a plurality of nanoparticle-containing composite layers and may be fused to one another via an automated process.

ORIGIN OF THE INVENTION

The invention described herein was made by employees of the United States Government and may be manufactured and used by or for the Government for Government purposes without payment of any royalties thereon or therefore.

FIELD OF THE INVENTION

The present disclosure relates to high quality thermoplastic composites containing nanoparticles and/or nanofibers, and to methods of producing such composites. The present disclosure also relates to methods of producing high quality nanoparticle-containing composite laminates.

BACKGROUND OF THE INVENTION

Thermoplastic composites are high strength material systems which are finding wide spread application in a variety of fields including aero structures, non-aero military structures, such as tanks and armored vehicles, and non-military structures such as automotive components, sporting goods, and industrial and medical devices. Typically, the composites comprise fiber reinforcements embedded in a resin matrix. Fiber reinforcements which have been contacted, e.g., coated and/or impregnated, with a resin are layered and joined to one another to form a composite laminate. Recently, automated lay-up of fiber-reinforced resin composites has replaced hand lay-up as a more economical and efficient method of producing composite laminates. Automated composite lay-up, such as heated head tape placement, filament winding, etc. requires the fiber-reinforced composites to have certain processing characteristics to produce high quality laminates. Additionally, there is an ongoing desire to improve the functional and mechanical properties of the laminates and to tailor these properties to specific applications.

SUMMARY OF THE INVENTION

In accordance with an embodiment, a nanoparticle-containing composite comprises a thermoplastic polymer matrix resin and a plurality of nanoparticles. In some embodiments, the composite may also include a fibrous structural reinforcement.

In accordance with another embodiment, a nanoparticle-containing composite laminate comprises a plurality of fused layers of nanoparticle-containing composites.

In accordance with yet another embodiment, a method of producing a nanoparticle-containing composite laminate comprises combining a thermoplastic polymer matrix resin with a plurality of nanoparticles to form a plurality of nanoparticle-containing composites, layering the plurality of nanoparticle-containing composites, and applying heat and/or pressure to the layered composites to fuse the composites. In some embodiments, the method may also include contacting a fibrous structural reinforcement with the thermoplastic polymer matrix resin and plurality of nanoparticles to form the plurality of nanoparticle-containing composites. Advantageously, in some embodiments the application of heat and/or pressure may be via an automated process.

Nanoparticle-containing thermoplastic composites and composite laminates, and methods of producing nanoparticle-containing thermoplastic composites and composite laminates provide numerous advantages in the art. For example, thermoplastic composites that are suitable for automated placement e.g., non-autoclave fabrication, provide an economical method to prepare high quality composite laminates cost effectively. Additionally, the size constraints imposed by autoclave fabrication may be eliminated allowing the nanoparticle-containing thermoplastic composite laminates to be utilized in a multitude of new applications.

Nanoparticle-containing thermoplastic composites and composite laminates may possess a variety of improved mechanical and functional properties. For example, thermoplastic composites having improved strength, modulus, impact resistance, toughness, conductivity, permeation resistance, and radiation absorption may be prepared according to the present embodiments. The disclosed nanoparticle-containing thermoplastic composites may have improved thermal and flame resistance, improved moisture and chemical resistance, increased hydrophobicity or oleophobicity, increased hydrophilicity or oleophilicity, and improved charge dissipation, and thermal/electrical conductivity. Additionally, the nanoparticle-containing thermoplastic composites may have unique and advantageous crystalline and/or amorphous properties. As an additional advantage, the presently disclosed nanoparticle-containing composite laminates may be particularly well-suited for automated processing. Automated processing, such as heated head placement and filament winding offer a low cost alternative to autoclave and press fabrication, and produce composites having properties that cannot be achieved using other processing methods. For example, automated tape laying processing provides extremely fast heat-up and cool down rates, and may allow unique crystalline and/or amorphous composite laminates to be formed.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Nanoparticle-containing composites, according to an embodiment, may comprise a thermoplastic polymer matrix resin and a plurality of nanoparticles. In some embodiments, the composites may further include a fibrous structural reinforcement.

The thermoplastic polymer matrix resin may comprise any of a multitude of thermoplastic polymers including those commonly used in the composites art. For example, thermoplastic polymers may include, but are not limited to: thermoplastic polyketones, including polyetherketones, such as PEEK and PEKK; polyethylene; polypropylene; polyimides, such as the ULTEM family of products available from G.E. Plastics, and the family of products available from IMITEC based on a license from NASA Langley Research Center; polyarylene ethers; polysulfones; polyamides, such as nylon; polyesters; polystyrene; acrylonitrile butadiene styrene (ABS); acrylic; celluloid; cellulose acetate; ethylene vinyl acetate (EVA); ethylene vinyl alcohol (EVAL); fluoroplastics, such as PTFE, FEP, PFA, CTFE, ECTFE, and ETFE; ionomers; liquid crystal polymers (LCP); polyacetal (POM or acrylonitrile); polyamide-imide (PAI); polyaryletherketone (PAEK); polybutadiene (PBD); polybutylenes; polybutylene terephthalate (PBT); polyethylene terephthalate (PET); polycyclohexylene dimethylene terephthalate (PCT); polycarbonate, polyhydroxyalkanoates (PHAs); polyester polyetherimide (PEI); polysulfones, including polyethersulfone; polyethylenechlorinates; polylactic acid; polymethylpentene; polyphenylene oxide; polyphenylene sulfide; polyphthalamide; polyvinyl chloride; polyvinylidene chloride; and mixtures thereof may be utilized in embodiments. Additional thermoplastic polymers which may be used include those which are suitable for carrying mechanical loads, resisting degradation at elevated temperatures, and/or resisting dissolution in solvents. The particular selection of a thermoplastic polymer depends on the desired end use for the composite, and is well within the ordinary skill of those in the art.

Thermoplastics are designed to melt, flow, and consolidate and are typically non-reactive. Thus, thermoplastics generally do not undergo a chemical reaction during processing and do not require additives such as curing agents, accelerators and hardeners. However, in some embodiments, one or more additives may be utilized to tailor the properties of the thermoplastic to the processing parameters. For example, in some embodiments, a flow modifier may be added to the thermoplastic polymer to adjust the melt viscosity of the polymer. The particular selection of a flow modifier may depend on the thermoplastic polymer being used and the method of processing, and is well within the ordinary skill of those in the art.

According to the present disclosure, the composite also includes a plurality of nanoparticles. The nanoparticles may be formed from any of a variety of materials. In many embodiments, the nanoparticles resist being melted, compressed or flattened when exposed to the pressures and temperatures encountered during processing, e.g., the nanoparticles remain rigid. Some exemplary materials from which the nanoparticles may be formed include, but are not limited to, inorganic materials, such as ceramics, silicons, and clays, and organic materials, such as carbon, including carbon nanotubes and carbon nanofibers. The particular selection of material may depend on the desired end use for the composite and the property enhancement desired. For example, in some embodiments, nanoparticles comprising carbon nanotubes may improve mechanical properties of a composite, such as strength, modulus, and toughness, and functional properties including conductivity and static discharge. A variety of nanoparticles are commercially available and the particular selection of nanoparticles for a particular application is well within the ordinary skill of those in the art.

The nanoparticles, according to embodiments, may have a multitude of configurations, including but not limited to: bead-like spheres, oblate spheroids, tubes, fibers, and/or one or more irregular shapes. The nanoparticles may have any size that does not adversely affect the melt flow of the thermoplastic polymer matrix resin. For example, the nanoparticles may have a particle size of less than about 999 nm, or less than about 700 nm, or less than about 500 nm, or as a further example, a particle size of less than about 200 nm.

The composites may include varying amounts of nanoparticles. For example, in some embodiments the nanoparticles may comprise from about 0.1 to about 40 wt % of the total composite, or from about 0.1 to about 25 wt %, or from about 0.1 to about 10 wt %, or as yet another example, from about 0.5 to about 5 wt % of the total composite. The particular amount may depend on a variety of factors, including for example, the property enhancement desired for the composite. For example, in some embodiments, one or more functional properties of a fiber reinforced composite may be improved by including carbon nanotubes in an amount ranging from about 0.1 to about 3 wt % of the total composite, while structural properties, such as tensile strength, may be improved by including carbon nanotubes in an amount ranging from about 3 to about 15 wt % of the total composite, and permeation in a composite may be reduced by including clay nanoparticles in an amount ranging from about 3 to about 15 wt % of the total composite. Another factor which may be considered in determining the amount of nanoparticles in the composite is whether the composite includes a fibrous structural reinforcement. For example, in some embodiments which do not include a fibrous structural reinforcement, the amount of nanoparticles may be greater than the amount in composites which do include a fibrous structural reinforcement.

In some embodiments, the nanoparticle-containing composite may include a fibrous structural reinforcement. A fibrous structural reinforcement may comprise fibers of varying lengths, including: continuous fibers, e.g., fibers having a length of greater than about 4 inches; long-discontinuous fibers, e.g., fibers having a length of from about 0.5 to about 4 inches; and discontinuous fibers, e.g., fibers having a length of less than about 0.5 inches. Continuous fiber structural reinforcements may have a variety of configurations including, for example, tapes or tows comprising uniformly disposed, parallel filaments and/or cloth woven from continuous fiber tow. Long-discontinuous fiber reinforcements may also have a variety of configurations including, for example, uniformly disposed, parallel filaments or cloth woven from long-discontinuous fiber tow. Similarly, a variety of discontinuous fiber structural reinforcements may be utilized, including, for example, random mats of discontinuous fibers.

Fibrous structural reinforcements, e.g., those comprising continuous fibers, long-discontinuous fibers, and/or discontinuous fibers, may comprise any of numerous kinds of fibers including synthetic and/or natural fibers. For example, in some embodiments, fibrous structural reinforcements may comprise one or more of: glass fibers and/or fibers formed of silicon carbide; alumina; titania; boron and the like; carbon and/or graphite fibers; as well as fibers formed from organic polymers, such as aromatic polyamides, polyethylenes, polyolefins, polyarylates, and polyaryl ethers. In an exemplary embodiment, the continuous fibrous structural reinforcement may comprise glass fibers, carbon fibers and/or aramid fibers such as the fibers sold by the DuPont Company under the tradename KEVLAR® or fibers sold by Tiejin under the tradename TWARON®.

The fibrous structural reinforcement, when present, may comprise varying proportions of the final composite. The proportion may be dependent on the end use envisioned, as well as the particular resin, fiber and processing method utilized. In some embodiments, the fibrous structural reinforcement may comprise from about 20 vol % or less to about 80 vol % or more of the total composite. For example, the fibrous structural reinforcement, when present, may comprise about 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75 or 80 vol % of the final composite, including any and all values and ranges therebetween.

Nanoparticle-containing composites may be produced, in some embodiments, by combining a plurality of nanoparticles with a thermoplastic polymer matrix resin. The plurality of nanoparticles may be combined with the thermoplastic polymer in a variety of ways, and preferably the method of combining achieves a substantially uniform dispersion of nanoparticles in the polymer. For example, the method of combining preferably results in the nanoparticles forming a substantially homogenous dispersion throughout the thickness of the polymer. In many embodiments, the nanoparticles may be combined with a thermoplastic polymer in a liquid state, such as a molten liquid state. Alternatively, the nanoparticles may be combined with a thermoplastic polymer matrix resin solution. In other embodiments, the nanoparticles may be combined with a thermoplastic polymer in a solid state, for example, the particles may be combined with a thermoplastic polymer in a powder form. In some embodiments, the nanoparticles may be sprayed or dispersed on the surface of the thermoplastic polymer. However, these embodiments do not typically achieve a substantially uniform dispersion of nanoparticles through the thickness of the polymer, but may be used in applications wherein a surface coating of particles achieves a desired property enhancement.

In some embodiments, the method of producing a nanoparticle-containing composite may also include contacting, e.g., impregnating, a fibrous structural reinforcement with the thermoplastic polymer matrix resin and the plurality of nanoparticles. In many embodiments, the thermoplastic polymer matrix resin and plurality of nanoparticles may be combined prior to contacting the fibrous structural reinforcement. However, in some embodiments, the fibrous structural reinforcement may be contacted with the thermoplastic polymer matrix resin and nanoparticles separately, e.g., prior to their being combined. For example, the fibrous structural reinforcement may be first contacted with the polymer matrix resin and subsequently contacted with the nanoparticles or alternatively, the fibrous structural reinforcement may be contacted with the nanoparticles and subsequently contacted with the polymer matrix resin.

The fibrous structural reinforcement may be impregnated with the thermoplastic polymer matrix resin or the combination of thermoplastic polymer matrix resin and nanoparticles using any of numerous methods ordinarily used for impregnating fiber reinforcements. For example, exemplary methods may include melt coating, calendaring, dip impregnation with a resin solution or molten resin, melt pressing the tape or fabric in a film of the nanoparticle-containing thermoplastic polymer or the like. A variety of factors may affect the choice of which method to utilize including, for example, the solubility of the thermoplastic polymer in a particular solvent and/or the viscosity of the polymer, and the particular selection is well within the ordinary skill of those in the field.

The nanoparticle-containing composites, according to the present disclosure, may be used to form multi-ply composite laminates. For example, a multi-ply composite laminate may comprise a plurality of nanoparticle-containing composites layered over one another. For example, a multi-ply composite laminate may include as few as two layers or as many as several hundreds of layers, e.g., about 200, 300, 400 or even more layers, depending on the desired end use. Individual layers may be from about 1 mil to about 20 mils thick. For example, layers formed using unidirectional tapes may be about 5 mils thick, while layers formed from woven fabrics may have a thickness greater than about 5 mils.

In many embodiments, the multi-ply composite laminate may comprise a plurality of layers of nanoparticle-containing composites that have been joined or fused to one another. For example, the layers may be fused to one another by the application of heat and/or pressure using any of the variety of methods and conventional processing devices and equipment ordinarily used for the production of layered composites. Advantageously, in many embodiments, the composite laminates may be formed using an automated process. However, in other embodiments, non-automated processes may be utilized. Some exemplary processing methods may include, but are not limited to: automated heated head tape placement; automated heated head tow placement; automated heated head fiber placement; automated heated head tape laying; automated fast tacking with automated heated head tape, tow, or fiber placement; automated fast tacking with autoclave post curing; automated fast tacking with automated tape laying or autoclave post curing; filament winding; roll forming; stretch forming; superforming; matched die forming; hydroforming; wet laying; panel thermoforming; in-line thermoforming; diaphragm forming; extrusion; pultrusion, sheet extrusion; injection molding; compression molding; resin transfer molding (RTM); rotation molding; blow molding; film casting; tow impregnation and consolidation; tape impregnation and consolidation; calendaring; foam processing; thermoplastic adhesive bonding; thermoplastic induction welding; thermoplastic resistance welding; thermoplastic focused infrared welding; thermoplastic ultrasonic welding; thermoplastic hot plate welding; thermoplastic vibration welding; thermoplastic laser welding; and/or thermoplastic microwave welding.

The use of the terms “a” and “an” and “the” and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms “comprising”, “having”, “including”, and “containing” are to be construed as open-ended terms (i.e., meaning “including, but not limited to,”) unless otherwise noted. The use of any and all exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-element claimed element as essential to the practice of the invention.

Preferred embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, the invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context. 

1. A nanoparticle-containing composite comprising a thermoplastic polymer matrix resin and a plurality of nanoparticles.
 2. The nanoparticle-containing composite according to claim 1 wherein said plurality of nanoparticles are substantially uniformly dispersed in said thermoplastic polymer matrix resin.
 3. The nanoparticle-containing composite according to claim 1 wherein said thermoplastic polymer matrix resin comprises a thermoplastic polymer selected from thermoplastic polyetherketones and thermoplastic polyimides.
 4. The nanoparticle-containing composite according to claim 1 wherein said plurality of nanoparticles is selected from carbon nanotubes, carbon nanofibers, inorganic nanoparticles, organic nanoparticles, and clay nanoparticles.
 5. The nanoparticle-containing composite according to claim 1 comprising from about 0.1 to about 40 weight percent of said nanoparticles.
 6. The nanoparticle-containing composite according to claim 1 wherein said nanoparticles have a particle size of less than about 999 nm.
 7. The nanoparticle-containing composite according to claim 6 wherein said nanoparticles have a particle size of less than about 200 nm.
 8. The nanoparticle-containing composite according to claim 1 further comprising a fibrous structural reinforcement.
 9. The nanoparticle-containing composite according to claim 8 wherein said fibrous structural reinforcement comprises fibers selected from continuous fibers, long-discontinuous fibers, discontinuous fibers, and mixtures thereof.
 10. The nanoparticle-containing composite according to claim 9 wherein said fibers are selected carbon fibers, glass fibers, organic fibers, and mixtures thereof.
 11. The nanoparticle-containing composite according to claim 8 comprising from about 20 to about 80 volume percent of said fibrous structural reinforcement.
 12. The nanoparticle-containing composite according to claim 8 wherein said plurality of nanoparticles is selected from carbon nanotubes, carbon nanofibers, inorganic nanoparticles, organic nanoparticles, and clay nanoparticles, and said composite comprises from about 0.1 to about 25 weight percent of said plurality of nanoparticles.
 13. The nanoparticle-containing composite according to claim 9 wherein said continuous fibers comprise one of uniformly disposed, parallel filaments of continuous fibers and cloth woven from continuous fibers.
 14. A nanoparticle-containing composite laminate comprising a plurality of fused layers of nanoparticle-containing composites.
 15. The nanoparticle-containing composite laminate according to claim 14 wherein said nanoparticle-containing composites comprise thermoplastic polymer matrix resin and a plurality of nanoparticles.
 16. The nanoparticle-containing composite laminate according to claim 15 wherein said nanoparticle-containing composites further comprise fibrous structural reinforcements,
 17. The nanoparticle-containing composite laminate according to claim 14 wherein said plurality of fused layers comprises from about 2 layers to about 400 layers of nanoparticle-containing composites.
 18. A method of producing a nanoparticle-containing composite laminate comprising combining a thermoplastic polymer matrix resin with a plurality of nanoparticles to form a plurality of nanoparticle-containing composites, layering the plurality of nanoparticle-containing composites, and applying heat and/or pressure to the layered composites to fuse the composites.
 19. The method of producing a nanoparticle-containing composite laminate according to claim 18 further comprising contacting a fibrous structural reinforcement with the thermoplastic polymer matrix resin and the plurality of nanoparticles to form the plurality of composite layers.
 20. The method of producing a nanoparticle-containing composite laminate according to claim 19 wherein the thermoplastic polymer matrix resin and plurality of nanoparticles are combined and the fibrous structural reinforcement is contacted with the combination of thermoplastic polymer resin and plurality of nanoparticles.
 21. The method of producing a nanoparticle-containing composite laminate according to claim 18 wherein applying heat and/or pressure to the layered nanoparticle-containing composites comprises an automated process.
 22. The method of producing a nanoparticle-containing composite laminate according to claim 21 wherein the automated process is selected from automated heated head tape placement, automated heated head tow placement, automated heated head fiber placement, and automated heated head tape laying. 